THE FREE-WILSON PARADIGM REDUX:SIGNIFICANCE OF THE FREE-WILSON COEFFICIENTS,INSIGNIFICANCE OF COEFFICIENT ‘UNCERTAINTIES’ AND STATISTICAL SINS

The Free-Wilson paradigm is an established and powerful tool for quantitatively relating activity withchemical structure.Current implementations of the paradigm,however,are flawed both conceptually andin execution.As part of an attempt to more fully realize the promise of the paradigm,it was necessaryto examine these limitations in detail.This report introduces a robust,theory-founded Free-Wilson implementation:stepwise principalcomponents regression analysis(SPCRA).SPCRA is computationally superior to previousimplementations but does not in itself correct their conceptual flaws.The development of SPCRA did,however,facilitate derivation of a simple and chemically significantinterpretation of the Free-Wilson structure-activity model.A number of statistical aspects of this modelcommonly misused in previous applications are discussed at length.These discussions provide criticalbackground for the development of an alternative implementation of the Free-Wilson paradigm.     

Vertical profiles of biospheric and fossil fuel-derived CO2 and fossil fuel CO2 : CO ratios from airborne measurements of Δ14C, CO2 and CO above Colorado, USA

Measurements of  Δ¹⁴C  in atmospheric CO₂ are an effective method of separating CO₂ additions from fossil fuel and biospheric sources or sinks of CO₂. We illustrate this technique with vertical profiles of CO₂ and  Δ¹⁴C  analysed in whole air flask samples collected above Colorado, USA in May and July 2004. Comparison of lower tropospheric composition to cleaner air at higher altitudes (>5 km) revealed considerable additions from respiration in the morning in both urban and rural locations. Afternoon concentrations were mainly governed by fossil fuel emissions and boundary layer depth, also showing net biospheric CO₂ uptake in some cases. We estimate local industrial CO₂:CO emission ratios using in situ measurements of CO concentration. Ratios are found to vary by 100% and average 57 mole CO₂:1 mole CO, higher than expected from emissions inventories. Uncertainty in CO₂ from different sources was ±1.1 to ±4.1 ppm for addition or uptake of −4.6 to 55.8 ppm, limited by  Δ¹⁴C  measurement precision and uncertainty in background  Δ¹⁴C  and CO₂ levels.     

Do the anomalous fluctuations of Sólheimajökull reflect ice-divide migration?

Ice-divide migration may explain the pattern of Holocene glacier fluctuations around the Mýrdalsjökull ice cap in southern Iceland. On at least three occasions Sölheimajokull, the principal outlet glacier on the southwest flank of the ice cap, has exceeded the Little Ice Age limits of recent centuries that mark the maximum extent of neighbouring glaciers in the Holocene. Bedrock divides beneath the Mýrdalsjökull ice cap do not coincide with present ice divides. It is suggested that the ice divide migrated during the course of ice-cap growth. At various stages during the Holocene (7000-4500, c. 3100, 1400-1200 BP) Sólheimajokull could have drained more of the ice cap than today, so becoming more advanced than neighbouring glaciers. In the Little Ice Age ( c. AD 1600–1900) the glacier could have had a smaller catchment as a result of ice-divide migration, resulting in a more inhibited advance compared with neighbouring glaciers which reached their Holocene maximum at that time. Identification of ice-divide migration is important for palaeoclimatic reconstructions because of the need to recognize different responses of glaciers to climate if one is to use their fluctuations as indicators of change.     

Lake Boksehandsken's earliest postglacial sediments and their palaeoenvironmental implications, Jameson Land, East Greenland

Lake Boksehandsken, the largest lake on Jameson Land, central East Greenland, is situated 54 m a.s.l. and holds a long (6.3 m) and complex stratigraphy. It was analysed with respect to lithology, carbon content, ¹⁴C, micro- and macrofossils. The diamict material in the bottom is overlain by a fining-upwards sequence, possibly deposited close to a receding ice margin in a glaciomarine environment. These deposits are interpreted to have been formed at the time of the marine limit ( c . 70 m) in the area. In spite of a large series of ¹⁴C datings, very few of the obtained dates were considered reliable. This is because the sediments contain coal fragments and old redeposited plant remains. Based on a set of arguments and correlations to the surrounding glacial stratigraphy it is implied that the marine limit and deglaciation cannot be much older than 10,000 BP. The lithology of the lake sediments, in combination with occurrence of marine macrofossils. shows that deglaciation was succeeded by a (glacio)marine depositional environment. The lake was isolated from the sea at c . 9000 BP. followed by a short transgression and a final isolation at c . 8400 BP. This sequence of events is demonstrated by both litho-and biostratigraphy and possible causes are discussed. A later oscillation some time between 8000 and 7500 BP. evidenced by litho-, carbon-, pollen- and Pecliastrum stratigraphy, is interpreted as a regional climatic cooling possibly correlatable to a distinct δ¹⁸O minima in the Greenland ice cores.     

Quaternary changes in level of the upper Taylor Glacier, Antarctica: implications for paleoclimate and East Antarctic Ice Sheet dynamics

Glacial drifts perched alongside outlet glaciers that drain through the Transantarctic Mountains constrain inland polar plateau ice elevations. The Taylor Glacier, which heads in the Taylor Dome (a peripheral dome of the East Antarctic Ice Sheet), drains East Antarctic ice into the Dry Valleys sector of Transantarctic Mountains and terminates in central Taylor Valley, about 24 km west of the Ross Sea. Five gravel-rich drifts (including 39 distinct moraine ridges) fringe a lateral lobe of the Taylor Glacier in the lower Arena Valley, Quartermain Mountains, southern Victoria Land. ³He and ¹⁰Be exposure age dating (from Brook et al . 1992), together with Arena Valley stratigraphy and soil morphologic data, provide chronologic control for these drifts and constrain maximum Quaternary thickening of the inland Taylor ice dome to less than 160 m. These minor Quaternary expansions of Taylor Glacier were out-of-phase with outlet glaciers that pass through the Transantarctic Mountains and terminate in the Ross Sea north and south of the Dry Valleys region. Textural analyses suggest that drift deposition occurred from cold-based ice, even though Taylor Glacier advances most likely occurred during global interglaciations. The thermal regime of former Taylor Glacier ice lobes, the character of geomorphic features superimposed on individual drifts, the chemical composition of soils developed on Taylor drifts, and the stability of in situ moraine ridges on steep valley walls suggest that the present cold-desert climate in Arena Valley has persisted for at least the last 2.2 Ma.     

Relative sea-level history and isostatic rebound in Newfoundland, Canada

The island of Newfoundland, Canada, is situated close to the former margins of the Laurentide ice sheet. The post-glacial sea-level history is complex, dominated by the effects of an ice-marginal crustal forebulge produced by isostatic deformation of the lithosphere. Marine fossils found above present sea-level can be ¹⁴C dated, and examination of the temporal and geographical distribution of these ¹⁴C dates in combination with geomorphological indicators of past sea-levels indicates regional trends of relative sea-level change. For most of the island (apart from the Northern Peninsula) no samples have been recovered that date younger than 8000 BP. suggesting that sea-level lay below the present one in these areas for the last 8000 years. The same areas commonly show geomorphological evidence for stands of sea-level both above and below present sea-level. This evidence is interpreted as showing that over most of Newfoundland, following deglaciation, sea-level fell to below present levels, and subsequently rose to the modern level. Exceptions to this pattern are the north of the Northern Peninsula, which shows a history of continuous emergence, or a more complex pattern of sea-levels falling below present, subsequently rising above present, and currently falling; and the northeast Avalon Peninsula, which may have had sea-levels below present throughout post glacial times. This pattern of relative sea-level change is interpreted as being mostly due to isostatic recovery, with the main factor being northerly migration of the forebulge. Mapping the time at which sea-level fell below the present level allows estimation of the rate of northerly migration and collapse of the forebulge at between 4.5 and 11 km/100 years; this is considerably faster than previous estimates.     

Flashfloods, earthquakes and uplift in the Pakistan Himalayas

Catastrophic flooding of parts of the frontal plains of the Pakistan Himalayas has occured throughout the historical past. The largest recorded flood (1841) originated from an earthquaketriggered landslip from the flanks of Nanga Parbat, which blocked the Indus river for six months. The earthquake probably occurred on the Liachar thrust, which has been responsible for uplifting the amphibolite facies Nanga Parbat gneisses to the Earth's surface in the last 10 million years. These movements raise serious problems for hydroelectric engineering project in this and other active mountain belts.